CN109486188A - Polyamic acid resin and polyamidoimide film - Google Patents
Polyamic acid resin and polyamidoimide film Download PDFInfo
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- CN109486188A CN109486188A CN201811043008.0A CN201811043008A CN109486188A CN 109486188 A CN109486188 A CN 109486188A CN 201811043008 A CN201811043008 A CN 201811043008A CN 109486188 A CN109486188 A CN 109486188A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/0009—Materials therefor
- G02F1/0063—Optical properties, e.g. absorption, reflection or birefringence
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08L2203/16—Applications used for films
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2203/00—Function characteristic
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Abstract
The invention discloses a kind of polyamic acid resins derived from aromatic diamine, aromatic dianhydride, alicyclic dianhydride and aromatic diacid chlorides and a kind of polyamidoimide film comprising the polyamidoimide derived from aromatic diamine, aromatic dianhydride, alicyclic dianhydride and aromatic diacid chlorides.
Description
Cross reference to related applications
According to the 119th section of 35 articles of United States Code No., this application claims mentioned on September 12nd, 2017 to Korean Intellectual Property Office
The priority for the 10-2017-0116249 South Korea patent application handed over, the disclosure of which are incorporated herein by reference in their entirety.
Technical field
Following disclosure is related to a kind of polyamic acid resin and a kind of polyamidoimide film.More specifically, following public
It opens content and is related to a kind of combined polyamic acid resin derived from specific components and a kind of comprising derived from specific components
The polyamidoimide film of combined polyamidoimide, with adjustable optical property and can be realized high-modulus.
Background technique
Under normal conditions, polyimides has excellent mechanical performance and hot property, therefore is applied to include being used to form
Various fields including the insulating substrate field of circuit and device.However, due to forming one kind between aromatic rings in polymerization
Charge-transfer complex makes polyimides become brown or yellow, causes the light transmittance of visible light region low, and therefore, it is difficult to will gather
Acid imide is applied to display material.
As the light transmittance for improving polyimides so that the colorless and transparent method of polyimides, a kind of use known in the art
The method that alicyclic diamine or aliphatic diamine inhibit the formation of Intramolecular electron transfer compound as diamine component.Japan
Special open 2002-161136 (patent document 1) disclose by by pyromellitic acid anhydride etc. aromatic acid dianhydride and
Anti-form-1, the polyimide precursor that 4- diaminocyclohexane is formed carry out imidizate and the polyimides that obtains, have height
Transparency but mechanical and physical performance deterioration.
Therefore, it as the yellow of polyimides to be converted into colorless and transparent method, has attempted to using various function lists
Body.However, since the polyimide film in visible light region with high transparency is in 400nm or shorter short wavelength region
Also there is high transparency value, therefore when film is exposed to ultraviolet light, is including the lower stepped construction of the display of polyimide film
Middle generation caused by ultraviolet light due to damaging.In order to solve this problem, intentionally using widely applied ultraviolet absorbing agent or
Ultra-violet stabilizer, however, polyimides is processed at high temperature so that it is difficult with additive, or even is using additive
In the case of, yellow colour index still increases.
Therefore, need to develop the technology of the polyimides with excellent intrinsic mechanical and physical performance at present, the performance is not
It can be deteriorated because realizing high-modulus, so that polyimides can be applied to various display material fields, and reduction can be passed through
Light transmittance in 400nm or shorter short wavelength region prevents from including the lower stepped construction of the display of polyimide film
Middle generation caused by ultraviolet light due to damaging, so as to further expansion coverage area.
[relevant technical literature]
[patent document]
(patent document 1) Japanese Unexamined Patent Publication 2002-161136 (on June 4th, 2002)
Summary of the invention
One embodiment of the invention is related to providing a kind of polyamic acid resin and a kind of polyamidoimide film, this is poly-
Amide imide film can be while with low yellow colour index with excellent mechanical and physical performance, and in visible light
There is excellent light transmittance in all-wave length region, realize low-transmittance in short wavelength region.
Particularly, one embodiment of the invention is related to providing a kind of polyamidoimide that can be realized high-modulus
Film.
In addition, one embodiment of the invention is related to providing a kind of polyamidoimide film, can prevent including
Occur in the substructure of the display of the polyamidoimide film by exposure to being damaged caused by ultraviolet light.
In a general aspect, polyamidoimide film includes being derived from aromatic diamine, aromatic dianhydride, alicyclic two
The polyamidoimide of acid anhydride and aromatic diacid chlorides, wherein the alicyclic dianhydride includes the compound indicated by following formula 1,
It is 88% or higher according to the total light transmittance that ASTM D1003 standard measures the polyamidoimide film, is measured at 388nm
Light transmittance is 40% or lower:
[chemical formula 1]
Wherein R1-R4It is independently from each other hydrogen, halogen, C1-C10Alkyl or C1-C10Alkoxy.
In accordance with an exemplary embodiment of the invention, aromatic diamine may include 2,2 '-bis- (trifluoromethyl)-benzidine.
In accordance with an exemplary embodiment of the invention, aromatic dianhydride may include the adjacent benzene two of 4,4 '-hexafluoroisopropylidenyl two
Formic anhydride and biphenyltetracarboxylic dianhydride.
In accordance with an exemplary embodiment of the invention, aromatic diacid chlorides may include paraphthaloyl chloride.
In accordance with an exemplary embodiment of the invention, based on the aromatic diamine of 100mol, the content of aromatic diacid chlorides
50mol can be greater than.
In accordance with an exemplary embodiment of the invention, based on the aromatic diamine of 100mol, the content of aromatic dianhydride can
Think 10-50mol.
In accordance with an exemplary embodiment of the invention, based on the aromatic diamine of 100mol, the content of aromatic dianhydride can
Be 5-25mol 4,4 '-hexafluoroisopropylidenyl diphthalic anhydrides and 5-25mol biphenyltetracarboxylic dianhydride.
In accordance with an exemplary embodiment of the invention, based on the aromatic diamine of 100mol, the content of alicyclic dianhydride can
Think 5-30mol.
In accordance with an exemplary embodiment of the invention, polyamidoimide film can have 5.0GPa or higher modulus, should
Modulus is measured by using the UTM 3365 for being purchased from Instron with the tensile speed of 25mm/min.
In accordance with an exemplary embodiment of the invention, according to ASTM E313 canonical measure, polyamidoimide film can have
3.0 or lower yellow colour index.
In accordance with an exemplary embodiment of the invention, the modulus of polyamidoimide film can be 5.0GPa or higher, should
Modulus by using the UTM 3365 for being purchased from Instron, with a thickness of 55 μm, length 50mm, width be 10mm sample, with
The tensile speed of 25mm/min measures.
In accordance with an exemplary embodiment of the invention, based on the film with a thickness of 55 μm, according to ASTM D1003 canonical measure,
The total light transmittance of polyamidoimide film is 88% or higher.
In accordance with an exemplary embodiment of the invention, based on the film with a thickness of 55 μm, according to ASTM E313 canonical measure,
Polyamidoimide film can have 3.0 or lower yellow colour index.
In accordance with an exemplary embodiment of the invention, based on the film with a thickness of 55 μm, the polyamide acyl that is measured at 388nm
The light transmittance of imines film can be 40% or lower.
In another general aspect, a kind of image display device includes polyamidoimide film as described above.
In another general aspect, a kind of polyamic acid resin is derived from aromatic diamine, aromatic dianhydride, alicyclic two
Acid anhydride and aromatic diacid chlorides, wherein the alicyclic dianhydride is indicated by following formula 1:
[chemical formula 1]
Wherein, R1-R4It is independently from each other hydrogen, halogen, C1-C10Alkyl or C1-C10Alkoxy.
In accordance with an exemplary embodiment of the invention, aromatic diamine may include 2,2 '-bis- (trifluoromethyl)-benzidine.
In accordance with an exemplary embodiment of the invention, aromatic dianhydride may include the adjacent benzene two of 4,4 '-hexafluoroisopropylidenyl two
Formic anhydride and biphenyltetracarboxylic dianhydride.
In accordance with an exemplary embodiment of the invention, aromatic diacid chlorides may include paraphthaloyl chloride.
According to the following detailed description, drawings and claims, other features and aspect be will be apparent.
Specific embodiment
Hereinafter, this hair is more fully described in the exemplary implementation scheme by reference including attached drawing and embodiment
It is bright.However, following exemplary embodiment and embodiment are only for detailed description of the present invention reference, the present invention is not limited to
This, and may be realized in various forms.
In addition, unless otherwise defined, all technical terms and scientific terms have and skill of the art
The identical meaning of the normally understood meaning of art personnel, terms used herein are only used for effectively describing certain illustrative implementations
Scheme, it is no intended to the limitation present invention.
Through the whole instruction of the invention is described, unless explicitly described to the contrary, otherwise any element of " comprising " will
It is construed as to imply that and further includes other element rather than exclude any other element.
In addition, unless be otherwise noted within a context, otherwise singular used in specification and appended
Plural form can also be intended to include.
In addition, " polyamic acid solution " is the solution formed by mix monomer in organic solvent, refer to containing logical
The polyamic acid resin that the monomer copolymerization crossed in organic solvent obtains.
The present inventor provides a kind of comprising aromatic diamine, aromatic dianhydride, alicyclic dianhydride and aromatic series
The polyamidoimide film of diacid chloride.That is, by by with certain aromatic diamines, dianhydride and aromatic diacid chlorides
Combined polyamic acid resin obtains polyamidoimide, and modulus can be shockingly excellent, and yellow colour index can be substantially reduced, and
And the light transmittance in total visible light region can be improved.Meanwhile discovery is by significantly reducing the light transmittance in short wavelength region, it can be with
A kind of polyamidoimide film is provided, can prevent from occurring in the substructure of display for including the polyamidoimide film
Due to being damaged caused by ultraviolet light, thereby completing the present invention.
Specifically, it can be applied to various show to provide by improving optical property and mechanical performance and hot property
The resin and film for showing field include certain aromatic diamines, aromatic dianhydride, alicyclic dianhydride and virtue the present invention provides one kind
The polyamic acid resin of fragrant race's diacid chloride, and a kind of polyamidoimide film as derived from it.
In accordance with an exemplary embodiment of the invention, the present invention relates to one kind comprising being derived from aromatic diamine, aromatic series
The polyamidoimide film of the polyamidoimide of dianhydride, alicyclic dianhydride and aromatic diacid chlorides, the wherein alicyclic dianhydride
Including the compound indicated by following formula 1, according to ASTM D1003 canonical measure, the total light transmission of the polyamidoimide film
Rate can be 88% or higher, and the light transmittance measured at 388nm is 40% or lower:
[chemical formula 1]
Wherein, R1-R4It is independently from each other hydrogen, halogen, C1-C10Alkyl or C1-C10Alkoxy.
Preferably, in accordance with an exemplary embodiment of the invention, the present invention relates to one kind comprising derived from aromatic diamine,
The polyamidoimide film of the polyamidoimide of aromatic dianhydride, alicyclic dianhydride and aromatic diacid chlorides, wherein aromatic series
Diamines includes 2,2 '-bis- (trifluoromethyl)-benzidine, and aromatic dianhydride may include 4,4 '-hexafluoroisopropylidenyl, two O-phthalic
Acid anhydrides and biphenyltetracarboxylic dianhydride, alicyclic dianhydride include the compound indicated by following formula 1, and aromatic diacid chlorides include
Paraphthaloyl chloride:
[chemical formula 1]
Wherein, R1-R4It is independently from each other hydrogen, halogen, C1-C10Alkyl or C1-C10Alkoxy.
In accordance with an exemplary embodiment of the invention, according to ASTM D1003 canonical measure, polyamidoimide film it is total
Light transmittance can be 88% or higher.Preferably, which can be 89% or higher.Specifically, which can
To be 88% to 99%.It is highly preferred that the total light transmittance can be 89-95%.Here it is possible to based on the sample with a thickness of 55 μm
Measure total light transmittance.
In addition, in accordance with an exemplary embodiment of the invention, polyamidoimide film can have 40% or lower
Light rate, the light transmittance are measured by using the UV-3600 purchased from Shimadzu and at 388nm.Preferably, it is surveyed at 388nm
The light transmittance obtained can be 30% or smaller.Specifically, the light transmittance measured at 388nm can be 1-40%.Preferably, exist
The light transmittance measured at 388nm can be 5-30%.Here it is possible to be measured at 388nm saturating based on the sample with a thickness of 55 μm
Light rate.
Polyamidoimide film comprising combined polyamidoimide present invention as described above has excellent mould
Amount, while significantly reducing yellow colour index and improving the light transmittance in the all-wave length region of visible light.Simultaneously as in short wavelength region
Middle light transmittance is substantially reduced, therefore can prevent from including polyamidoimide film in the case where no ultraviolet light additive
Display substructure in occur due to being damaged caused by ultraviolet light.In addition, due to being free of ultraviolet light additive,
It can prevent the physical property of polyamidoimide from deteriorating, therefore the preferably film.
In accordance with an exemplary embodiment of the invention, alicyclic dianhydride may include the compound indicated by following formula 1:
[chemical formula 1]
Wherein, R1-R4Hydrogen, halogen, C can be independently from each other1-C10Alkyl or C1-C10Alkoxy.
Preferably, in chemical formula 1, R1-R4It can independently of one another be hydrogen or C1-C10Alkyl.
It is highly preferred that in chemical formula 1, R1-R4It can independently of one another be hydrogen or C1-C5Alkyl.
Most preferably, specifically, such as, it may include 1,2,3,4- cyclobutane tetracarboxylic dianhydride (CBDA).
When comprising the alicyclic dianhydride, passing through aromatic diamine as described above, aromatic dianhydride and aromatic series
In the polyamidoimide film of the combination preparation of diacid chloride, low yellow colour index may be implemented, and visible light region can be improved
In light transmittance, be therefore preferred.
In accordance with an exemplary embodiment of the invention, based on the aromatic diamine of 100mol, the content of alicyclic dianhydride can
Think 5-30mol.Preferably, which can be 5-20mol.When containing alicyclic dianhydride with above-mentioned content, yellow colour index
It significantly reduces, and the light transmittance in the all-wave length region of visible light can be improved, be therefore preferred.
The aromatic diamine of exemplary implementation scheme may include 2,2 '-bis- (trifluoromethyl)-benzidine according to the present invention.It is logical
The charge transfer effect of fluoro substituents is crossed, aromatic diamine can assign excellent optical property, and 2,2 '-bis- (fluoroforms
Base)-benzidine can provide polyamidoimide, and it is the group using aromatic dianhydride, alicyclic dianhydride and aromatic diacid chlorides
Close the product that imidizate is carried out to polyamic acid resin, thus realize the required optical property changed with wavelength region and
Excellent mechanical and physical performance.
Here, aromatic diamine can pass through 2,2 '-bis- (trifluoromethyl)-benzidine of mixing and other known aromatic series
Diamine components are come using however, it is more preferred to be used alone 2,2 '-bis- (trifluoromethyl)-benzidine realize effect to be achieved.
The dianhydride of exemplary implementation scheme includes aromatic dianhydride and alicyclic dianhydride according to the present invention.
Aromatic dianhydride of the invention is specifically for example selected from 4,4 '-hexafluoroisopropylidenyl diphthalic anhydrides (6-
FDA), biphenyltetracarboxylic dianhydride (BPDA), 1,2,4,5 benzenetetracarboxylic acid dianhydride (PMDA), benzophenone tetracarboxylic dianhydride
(BTDA), 4,4 '-oxygen, two O-phthalic acid dianhydride (ODPA), bis- (di carboxyl phenyloxy) diphenyl ether dianhydrides (BDSDA),
Any one of TBIS-BAN (CAS 867350-98-9) and TBIS-MPN (CAS 933041-59-9) etc. or two or
Multiple mixtures.More preferably come using only 4,4 '-hexafluoroisopropylidenyl diphthalic anhydrides and biphenyltetracarboxylic dianhydride real
Existing required physical property effect.
Aromatic diamine based on 100mol, the content of the aromatic dianhydride of exemplary implementation scheme can be with according to the present invention
For 10-50mol.Preferably, which can be 10-40mol.It is highly preferred that the content can be 20-40mol.
It is highly preferred that the aromatic diamine based on 100mol, the aromatic dianhydride of exemplary implementation scheme according to the present invention
Content can be the 4,4 '-hexafluoroisopropylidenyl diphthalic anhydrides of 5-25mol and the biphenyltetracarboxyacid acid two of 5-25mol
Acid anhydride.Preferably, which can be the 4 of 10-20mol, the connection of 4 '-hexafluoroisopropylidenyl diphthalic anhydrides and 10-25mol
Benzene tertacarbonic acid's dianhydride.In the range of the content, when preparing polyamidoimide film, the light transmittance in short wavelength region obviously drops
It is low, and can prevent include polyamidoimide film display substructure in occur due to ultraviolet light caused by
Damage, this is preferred.
In accordance with an exemplary embodiment of the invention, aromatic diacid chlorides include paraphthaloyl chloride, are used for and fragrance
Race's diamine reactant in macromolecular chain to form amide structure.In addition, it may further comprise other known aromatic diacid chlorides.Specifically
Ground, it is, for example, possible to use any one in Isosorbide-5-Nitrae-naphthalene dimethyl chloride, 2,6- naphthalene dimethyl chloride and 1,5- naphthalene dimethyl chloride etc.
A or two or more mixture.It is preferred that paraphthaloyl chloride is used alone, according to the range tune of polyamidoimide film
Optical property is saved, and also significantly improves modulus.
In accordance with an exemplary embodiment of the invention, based on the aromatic diamine of 100mol, the content of aromatic diacid chlorides
50mol can be greater than.Preferably, which can be 55mol or more.Specifically, which can be 55-90mol, preferably
55-80mol, more preferable 55-75mol.
Balance of physical properties when content is met the above range, needed for being realized by the combination of other components, that is,
There is high transparency in the entire area of visible light, without causing mechanical performance and thermophysical property to deteriorate.In addition, also by
Low-transmittance is realized in 400nm or shorter short wavelength region, can prevent from including the display of polyamidoimide film
Occur in substructure due to being damaged caused by ultraviolet light.Furthermore it is possible to further decrease yellow colour index, and may be implemented
Significantly improve the synergistic effect of modulus.
By being copolymerized the aromatic diacid chlorides of high-content as described above, polyamidoimide film prepared therefrom has aobvious
Improved optical property is write, while high-modulus may be implemented, this is preferred.
Particularly, due to there is gelation etc. during carrying out polymerization reaction with diamines, it is difficult to be higher than using content
The aromatic diacid chlorides of 50mol.Therefore, it is generally the case that in order to use the aromatic diacid chlorides of high-content, lithium chloride, chlorination
Calcium etc. is used together, however, the chloride ion that these compounds leave can generate adverse effect to environment or make the physical of film
It can deterioration.In order to solve these problems, in the present invention it is possible to according to include aromatic diamine, aromatic dianhydride and alicyclic ring
The combination of other components including race's dianhydride adjusts ratio of components, and adjusts the polymerization concentration of reaction sequence and reactive component with aobvious
The content for increasing aromatic diacid chlorides is write, thus the physical property effect needed for realizing.
Since the foregoing describe the tools of above-mentioned aromatic diamine, aromatic dianhydride, alicyclic dianhydride and aromatic diacid chlorides
Body example and content etc., therefore be described in detail omitting.
It in the present invention, can be preferably by as the polyamic acid resin for preparing the precursor before polyamidoimide
It is copolymerized the resin of aromatic diamine, aromatic dianhydride, alicyclic dianhydride and aromatic diacid chlorides preparation.
Specifically, a kind of polyamic acid resin can be provided, wherein aromatic diamine includes 2,2 '-bis- (trifluoromethyls)-
Benzidine, aromatic dianhydride include 4,4 '-hexafluoroisopropylidenyl diphthalic anhydrides and biphenyltetracarboxylic dianhydride, alicyclic two
Acid anhydride includes the compound indicated by following formula 1, and aromatic diacid chlorides include paraphthaloyl chloride.
[chemical formula 1]
Wherein, R1-R4Hydrogen, halogen, C can be independently from each other1-C10Alkyl or C1-C10Alkoxy.
In the present invention, aromatic diamine and the mixture of aromatic dianhydride, alicyclic dianhydride and aromatic diacid chlorides
Equivalent proportion is preferably 0.9:1 to 1.1:1, more preferably 1:1.When meeting the range, when by the polyamides for being derived from monomer
Amino acid resin carries out imidizate and when the polyamidoimide that obtains forms film, film it is physical including filming performance
It can be improved, this is preferred.
Polyamic acid resin can be provided in the form of the polyamic acid solution of dissolution in a solvent, which is
The solution of above-mentioned monomer, and may include the organic solvent for solution polymerization.To the no spy of the type of organic solvent
It does not limit, specifically, for example, it is preferable to using dimethyl acetamide (DMAc), N-Methyl pyrrolidone (NMP), dimethyl is selected from
Any one of formamide (DMF), dimethyl sulfoxide (DMSO), acetone, diethyl acetamide, metacresol etc. or two kinds or more
Kind.
In the present invention, the polyamic acid solution comprising polyamic acid resin and solvent can be by removing polyamic acid resin
It in addition further comprise any one of the imidization catalyst being selected from and dehydrating agent or two or more carry out acid imide
Change.
It can be used any one or more of as imidization catalyst selected from pyridine, isoquinolin and β-quinoline.Separately
Outside, can be used it is any one or more of as dehydrating agent selected from acetic anhydride, phthalic anhydride and maleic anhydride, but need not
It is confined to this.
Based on 1mol aromatic dianhydride and alicyclic dianhydride, the embodiment party exemplary according to the present invention of 1-5mol may include
Case is selected from any one of imidization catalyst and dehydrating agent or two or more of mixtures.Preferably, may include
1.5-3mol, but not limited to this.
In the present invention, polyamic acid solution imidizate can be obtained to polyamidoimide film.Wherein, acid imide
Change can be used known imidizate method and carry out.Chemical imidization is preferred.More preferably by the inclusion of pyridine and second
Acid anhydrides carrys out chemical imidization polyamic acid solution.
Polyamic acid solution according to the present invention can further comprise various forms of additives.It may further include choosing
Any from fire retardant, bonding improver, inorganic particle, antioxidant, ultraviolet inhibitor, plasticizer, antistatic agent etc.
It plants or two or more is as additive, but not limited to this.
In addition, the present invention provides a kind of image display device including above-mentioned polyamidoimide film.
The present invention provides a kind of preparation method of polyamidoimide film comprising following steps:
(a) in organic solvent by aromatic diamine dissolution, be then added aromatic dianhydride thereto, alicyclic dianhydride and
Aromatic diacid chlorides are reacted to prepare polyamic acid solution；
(b) imidizate polyamic acid solution is to prepare polyamidoimide；And
(c) polyamide coating imide solution, wherein polyamidoimide dissolves in organic solvent.
In the present invention, the method for preparing polyamidoimide film is not particularly limited, it is however preferred to use equipped with
Blender, nitrogen injection device, Dropping feeder, temperature controller and cooler reactor implement this method.
In accordance with an exemplary embodiment of the invention, the step of preparing polyamic acid solution (a) may include in reactor
Middle addition organic solvent, dissolves aromatic diamine wherein, then reacts aromatic dianhydride and alicyclic dianhydride, is then added
Aromatic diacid chlorides are reacted.
In addition, another exemplary implementation scheme of the step of preparing polyamic acid solution (a) can be for into reactor
Organic solvent is added, dissolves aromatic diamine wherein, is then reacted with aromatic diacid chlorides, then make aromatic dianhydride and rouge
Two anhydride reactant of ring race.This be it is furthermore preferred that because the contents of aromatic diacid chlorides can increase in finally obtained polymer,
That is, although solid content is high, polymerization reaction uniformity is also excellent, and other than excellent optical property, it can also be real
Existing high-modulus.
In accordance with an exemplary embodiment of the invention, when preparing polyamic acid solution, by by aromatic diamine gradually
It is added in organic solvent rather than is once all added to be reacted, to improve reactivity.Additionally, it is preferred that first will be fragrant
Race's diamines is added in organic solvent, then dissolves aromatic diamine sufficiently.Wherein, organic solvent used as described above,
It is preferable to use dimethyl acetamide or n-methyl-2-pyrrolidone.Furthermore, it is contemplated that as the copolymerization product derived from monomer
The molecular weight of polyamidoimide can properly select the content of organic solvent, can be 80- in entire composition
97wt%.Content is preferably 85-95wt%, more preferably 87-95wt%.That is, solid content is 3-20wt%, preferably 5-
15wt%, more preferable 5-13wt%.
When the content of organic solvent is less than 80wt%, gelation may occur in the course of the polymerization process, it may be difficult to obtain
Uniform solution, and being formed has the highly viscous solution beyond usable range, so carrying out purifying using solvent may be not
It is easy.Therefore, when that cannot be purified well, the optical property of such as light transmittance and yellow colour index may be bad in film forming
Change.In addition, when the content of organic solvent is greater than 97wt% solution can be formed, but the yield of polyamidoimide may
It can reduce.
Step (a) carries out under inert gas atmosphere, specifically, for example, having nitrogen or argon return in the reactor
Under the conditions of carry out.In addition, range of reaction temperature is room temperature to 80 DEG C, especially 20-80 DEG C, the reaction time is 30 minutes to 24 small
When, but not limited to this.
Imidation step (b) is the polyamic acid solution imidizate that will prepare in step (a) to obtain polyamide acyl
Imines can apply known imidizate method, for example, hot-imide method, chemical imidization method and hot acyl
The combination of imidization method and chemical imidization method.It is preferred that make solution chemistry imidizate, but not limited to this.
In addition, imidizate can carry out before or after polyamide coating imide solution, and can be by known
Various methods implement, therefore it is unrestricted.
In the present invention, chemical imidization can further comprise being selected from acyl by the polyamic acid solution in preparation
Any one of imidization catalyst and dehydrating agent or two or more carry out.According to obtained polyamidoimide
Physical property, preferably by will selected from any one of imidization catalyst and dehydrating agent or two or more be added to step
(a) in the polyamic acid solution prepared in, Lai Jinhang chemical imidization.It is highly preferred that will selected from imidization catalyst and
Any one of dehydrating agent or two or more be added in polyamic acid solution to carry out imidizate, then using solvent into
To obtain solid component, which is dissolved and obtains polyamideimide solution in a solvent for row purifying.
Wherein it is possible to use any one or more of as de- selected from acetic anhydride, phthalic anhydride and maleic anhydride
Aqua, and can be used it is any one or more of as imidization catalyst selected from pyridine, isoquinolin and β-quinoline, but
It is without being limited thereto.
In accordance with an exemplary embodiment of the invention, it is preferable to use can obviously reduce the molten of polyamidoimide solid component
The solvent of Xie Du, it is especially for example any one or more of selected from water and alcohol, after imidizate polyamic acid solution
Solvent used in purifying.
When the solid component for obtaining polyamidoimide by purifying, it is then dissolved in organic solvent to obtain acid imide
When the polyamidoimide of change, as organic solvent to be used, what is used when can be used and prepare polyamic acid is organic molten
The identical or different solvent of agent.Wherein, the content of solvent can be 70-95wt%.Content is preferably 75-95wt%, more preferably
80-90wt%.
In addition, when measurement is by dissolving the polyamidoimide prepared in a solvent for the polyamidoimide finally obtained
When the viscosity of solution, viscosity can be 5,000-500,000cps, preferably 8,000-300,000cps, more preferable 10,000-
200,000cps.Herein, viscosity is measured at 25 DEG C using Brookfield viscosimeter.
The weight average molecular weight for the polyamidoimide that the present invention obtains is 50,000-1,000,000g/mol, preferably 50,
000-800,000g/mol, more preferable 50,000-500,000g/mol.Wherein, the measurement of weight average molecular weight uses polystyrene
As standard sample, using the 1260Infinity for being purchased from Anjelen Sci. & Tech. Inc (Agilent Technologies),
Wherein use PL gel Olexis column, and the DMAc of the LiCl using the 100ml 0.5wt% of the polyamidoimide containing 4mg
Solution is as sample.In addition, the glass transition temperature of polyamidoimide can be 200-400 DEG C, preferably 320-390 DEG C.
It may further include step (c): polyamide coating imide solution, the polyamides in the polyamideimide solution
Amine acid imide dissolves in a solvent, and is heat-treated to the solution of coating.Heat treatment step includes that polyamidoimide is molten
Liquid is cast on the substrate of such as glass substrate, and is heat-treated cast-solution to form film.Wherein, institute in step (c)
The term " polyamideimide solution " stated refers to the coating for being used to prepare the film of the polyamidoimide containing polyamidoimide
Composition.
In accordance with an exemplary embodiment of the invention, it is preferably gradually heat-treated as example.Preferably, heat treatment can
Gradually to be carried out 1 minute to 2 hours at 80-100 DEG C, gradually carried out 1 minute to 2 hours at 100-200 DEG C, Huo Zhe
It is gradually carried out 1 minute to 2 hours at 250-300 DEG C.It is highly preferred that carrying out 30 points according to the gradually heat treatment of respective temperature range
Clock was to 2 hours.Wherein, it is further preferred that when proceeding to each step, by being heated in the range of preferred 1-20 DEG C/min
To be gradually heat-treated.In addition, heat treatment can carry out in individual vacuum drying oven, but it need not be confined to this.
In accordance with an exemplary embodiment of the invention, it is contemplated that the thickness of prepared film can be used spreader and be applied
Coated with forming film on substrate, and the thickness of film can be 10-100 μm, preferably 20-90 μm, but not limited to this.
In accordance with an exemplary embodiment of the invention, polyamidoimide film can have 5.0GPa or higher modulus, should
Modulus uses the UTM 3365 purchased from Instron to measure with the tensile speed of 25mm/min.Specifically, modulus can be 5.0-
10GPa, preferably 5.0-8.0GPa.Wherein it is possible to based on being 50mm with a thickness of 55 μm, length and sample that width is 10mm is surveyed
Measure modulus.
In addition, in accordance with an exemplary embodiment of the invention, according to ASTM D1003 canonical measure, polyamidoimide film
Total light transmittance can be 88% or higher.Preferably, which can be 89% or higher.Specifically, the total light transmission
Rate can be 88%-99%.Preferably, which can be 89%-95%.Wherein it is possible to based on a thickness of 55 μm
Sample measures total light transmittance.
In addition, in accordance with an exemplary embodiment of the invention, being surveyed at 388nm using the UV-3600 purchased from Shimadzu
Amount, polyamidoimide film can have 40% or lower light transmittance.Preferably, light transmittance can be 30% or lower.Tool
Body, the light transmittance measured at 388nm can be 1-40%.Preferably, light transmittance can be 5-30%.Wherein it is possible to base
The light transmittance at 388nm is measured in the sample with a thickness of 55 μm.
In addition, the yellow colour index of polyamidoimide film can be 3.00 or lower according to ASTM E313 canonical measure,
Preferably 2.60 or lower.Specifically, yellow colour index can be 1.00-3.00, preferably 1.00-2.60.Wherein, yellow colour index makes
It is measured with the ColorQuest XE measuring device purchased from HunterLab.Furthermore, it is possible to based on the sample measurement with a thickness of 55 μm
Yellow colour index.
As described above, can be realized the polyamidoimide film of superior physical properties can be derived from aromatic diamine, virtue
Fragrant race's dianhydride, alicyclic dianhydride and aromatic diacid chlorides.Specifically, which can be by the polyamide derived from polyamic acid resin
Acid imide provides, and wherein aromatic diamine includes 2,2 '-bis- (trifluoromethyl)-benzidine, and aromatic dianhydride includes 4,4 '-hexafluoros
Isopropylidene diphthalic anhydrides and biphenyltetracarboxylic dianhydride, alicyclic dianhydride include the chemical combination indicated by following formula 1
Object, and aromatic diacid chlorides include paraphthaloyl chloride.
[chemical formula 1]
Wherein R1To R4It is independently from each other hydrogen, halogen, C1-C10Alkyl or C1-C10Alkoxy.
All total light transmittances high as discussed may be implemented by the polyamidoimide film of combination preparation and low yellow refers to
Several optical properties, and also there is excellent modulus, and the light transmittance in short wavelength region can be reduced.
The present invention can be used polyamidoimide and manufacture various forms of mechanographs.As example, the present invention can be answered
For including film, the printed wiring board of protective film or insulating film, flexible circuit board etc., but not limited to this.Preferably, the present invention can
It is had a wide range of applications applied to the protective film that can replace glass cover-plate, and in the various industrial circles for including display
Range.
Hereinafter, by description the preferred embodiment of the present invention and comparative example.However, following embodiment is only preferably to show
Example property embodiment, the present invention is not limited thereto.
Physical property of the invention is measured as follows:
(1) light transmittance (unit: %)
Using the COH-400 for being purchased from Nippon Denshoku Industries Co., Ltd. (Nippon Denshoku), according to ASTM D1003
The total light transmittance of the film prepared in canonical measure embodiment and comparative example.It is measured and is implemented using the UV-3600 purchased from Shimadzu
Light transmittance of the film prepared in example and comparative example at 388nm.
(2) yellow colour index
Use the ColorQuest XE (mode type: total transmissivity, observation area: 0.375 for being purchased from HunterLab manufacturing company
Inch, UV filter: nominal), according to the yellow colour index of the film prepared in ASTM E313 canonical measure embodiment and comparative example.
(3) modulus
Using be purchased from Instron UTM 3365, under 25 DEG C and 25mm/min of stretching condition measure embodiment and
The modulus for the film that the length prepared in comparative example is 50mm, width is 10mm.
(4) viscosity
Viscosity is measured at 25 DEG C using Brookfield viscosimeter (Dv2TRV-cone&plate, CPA-52Z).
(5) molecular weight
Using the 1260Infinity for being purchased from Anjelen Sci. & Tech. Inc, weight is measured using polystyrene as standard sample
Average molecular weight, wherein using PL gel Olexis column, and the 100ml 0.5wt% for the use of polyamidoimide content being 4mg
The DMAc solution of the LiCl of concentration is as sample.
Embodiment 1
Under nitrogen atmosphere, by methylene chloride and 2,2 '-bis- (trifluoromethyl)-benzidine (TFMB) are added in reactor simultaneously
It is sufficiently stirred, paraphthaloyl chloride (TPC) then is added thereto, stir 6 hours to dissolve and be reacted.Hereafter, it uses
Excessive methanol is precipitated and is filtered to obtain reaction product, it is dried in vacuo 6 hours at 50 DEG C or the longer time, and
DMAc is added in reactor again in a nitrogen atmosphere, 4,4 '-hexafluoroisopropylidenyl diphthalic anhydrides are added thereto
(6FDA) is sufficiently stirred until dissolution, is then added biphenyltetracarboxylic dianhydride (BPDA), then ring is added until dissolution in stirring
Butane tetracarboxylic acid dianhydride (CBDA), and stir until dissolution.Then, by pyridine and acetic anhydride with 2.5 times of the total additional amount of dianhydride
Mol amount be added solution in, stirred 1 hour at 60 DEG C.Wherein, the amount of each monomer makes TFMB:BPDA:CBDA:6FDA:
The mol ratio of TPC is 100:10:20:15:55, and solution is adjusted to the solid content with 12wt%.It uses
Brookfield viscosimeter measures at 25 DEG C, and the viscosity of finally obtained polyamidoimide is 33,000cps.
Acquired solution is subjected to solution-cast on the glass substrate using spreader.Then, in vacuum drying oven, 100
It is heat-treated 30 minutes at DEG C, is heat-treated 30 minutes at 200 DEG C, be heat-treated 30 minutes at 300 DEG C, then carry out at room temperature
It is cooling, the film formed on the glass substrate is separated with substrate, obtains the polyamidoimide film with a thickness of 55 μm.Measure film
Weight average molecular weight, result 205,000g/mol.
Embodiment 2
Other than the mol of TFMB:BPDA:CBDA:6FDA:TPC ratio is 100:20:10:15:55, with same as Example 1
Mode prepare the polyamidoimide film with a thickness of 56 μm.The weight average molecular weight of prepared polyamidoimide is 195,000g/
Mol is measured at 25 DEG C using Brookfield viscosimeter, and the viscosity of finally obtained polyamidoimide is 27,000cps.
Embodiment 3
In addition to the mol of TFMB:BPDA:CBDA:6FDA:TPC ratio be 100:10:5:15:70 other than, with 1 phase of embodiment
Same mode prepares the polyamidoimide film with a thickness of 56 μm.The weight average molecular weight of prepared polyamidoimide is 210,
000g/mol is measured at 25 DEG C using Brookfield viscosimeter, and the viscosity of finally obtained polyamidoimide is 30,
000cps。
Embodiment 4
In addition to the mol of TFMB:BPDA:CBDA:6FDA:TPC ratio be 100:15:10:15:60 other than, with 1 phase of embodiment
Same mode prepares the polyamidoimide film with a thickness of 55 μm.The weight average molecular weight of prepared polyamidoimide is 190,
000g/mol is measured at 25 DEG C using Brookfield viscosimeter, and the viscosity of finally obtained polyamidoimide is 28,
000cps。
Embodiment 5
In addition to do not use biphenyltetracarboxylic dianhydride (BPDA), and further comprise by following formula 2 indicate chemical combination
Object makes the mol ratio of TFMB:TBIS-MPN:CBDA:6FDA:TPC be except 100:5:25:15:55, with same as Example 1
Mode prepare the polyamidoimide film with a thickness of 60 μm.The weight average molecular weight of prepared polyamidoimide is 195,
000g/mol is measured at 25 DEG C using Brookfield viscosimeter, and the viscosity of finally obtained polyamidoimide is 28,
000cps。
[chemical formula 2]
Embodiment 6
In addition to do not use biphenyltetracarboxylic dianhydride (BPDA), and further comprise by following formula 3 indicate chemical combination
Object makes the mol ratio of TFMB:TBIS-BAN:CBDA:6FDA:TPC be except 100:5:25:15:55, with same as Example 1
The polyamidoimide film that mode is prepared with a thickness of 58 μm.The weight average molecular weight of prepared polyamidoimide is 170,000g/
Mol is measured at 25 DEG C using Brookfield viscosimeter, and the viscosity of finally obtained polyamidoimide is 21,000cps.
[chemical formula 3]
Embodiment 7
In addition to not using biphenyltetracarboxylic dianhydride (BPDA), the mol ratio of TFMB:CBDA:6FDA:TPC is 100:30:15:
55, and further comprise ultraviolet (UV) additive (TBO, 2,5- bis- (the tertiary fourths of 5- of the 0.15wt% of the total amount based on composition
Base -2- benzoxazolyl) thiophene) except, the polyamidoimide with a thickness of 50 μm is prepared in the same manner as example 1
Film.The weight average molecular weight of prepared polyamidoimide is 220,000g/mol, using Brookfield viscosimeter at 25 DEG C
Lower measurement, the viscosity of finally obtained polyamidoimide are 58,000cps.
Comparative example 1
In addition to not using biphenyltetracarboxylic dianhydride (BPDA), and the mol ratio of TFMB:CBDA:6FDA:TPC is 100:20:
Except 25:55, the polyamidoimide film with a thickness of 50 μm is prepared in the same manner as example 1.Prepared polyamide
Imido weight average molecular weight is 190,000g/mol, is measured at 25 DEG C using Brookfield viscosimeter, finally obtained
The viscosity of polyamidoimide is 35,000cps.
Comparative example 2
In addition to not using cyclobutane tetracarboxylic dianhydride (CBDA), and the mol ratio of TFMB:BPDA:6FDA:TPC is 100:20:
Except 25:55, the polyamidoimide film with a thickness of 58 μm is prepared in the same manner as example 1.Prepared polyamide
Imido weight average molecular weight is 180,000g/mol, is measured at 25 DEG C using Brookfield viscosimeter, finally obtained
The viscosity of polyamidoimide is 32,000cps.
Comparative example 3
In addition to not using 4,4 '-hexafluoroisopropylidenyl diphthalic anhydrides (6FDA), and TFMB:BPDA:CBDA:TPC
Mol ratio be 100:20:20:60 except, implement this method in the same manner as example 1, however, solution hardening be muddiness
Opaque state, therefore it is unable to measure viscosity and weight average molecular weight.
Comparative example 4
In addition to without using biphenyltetracarboxylic dianhydride (BPDA) and cyclobutane tetracarboxylic dianhydride (CBDA) and TFMB:6FDA:
The mol ratio of TPC is to prepare the polyamidoimide with a thickness of 55 μm in the same manner as example 1 except 100:30:70
Film.The weight average molecular weight of prepared polyamidoimide is 150,000g/mol, using Brookfield viscosimeter at 25 DEG C
Lower measurement, the viscosity of finally obtained polyamidoimide are 15,000cps.
Comparative example 5
It in addition to not using biphenyltetracarboxylic dianhydride (BPDA), and further comprise the compound indicated by following formula 4
So that the mol ratio of TFMB:BPAF:CBDA:6FDA:TPC is except 100:10:20:15:55, in the same manner as example 1
Prepare the polyamidoimide film with a thickness of 59 μm.The weight average molecular weight of prepared polyamidoimide is 160,000g/
Mol is measured at 25 DEG C using Brookfield viscosimeter, and the viscosity of finally obtained polyamidoimide is 18,000cps.
[chemical formula 4]
Comparative example 6
It in addition to not using biphenyltetracarboxylic dianhydride (BPDA), and further comprise aromatic series 3,4- oxydiphenyl amine (3,4-
ODA), so that the mol ratio of TFMB:3,4-ODA:CBDA:6FDA:TPC are except 90:10:30:15:55, with same as Example 1
The polyamidoimide film that mode is prepared with a thickness of 52 μm.The weight average molecular weight of prepared polyamidoimide is 195,000g/
Mol is measured at 25 DEG C using Brookfield viscosimeter, and the viscosity of finally obtained polyamidoimide is 30,000cps.
As shown in table 1, it was demonstrated that embodiment according to the present invention has excellent total light transmittance, low yellowness index and Gao Mo
Amount.Particularly, it was demonstrated that the light transmittance measured at 388nm is low.It is particularly preferred that when aromatic diamine includes 2,2 '-bis- (three
Methyl fluoride)-benzidine, and aromatic dianhydride includes 4,4 '-hexafluoroisopropylidenyl diphthalic anhydrides and biphenyltetracarboxyacid acid
Dianhydride, when alicyclic dianhydride includes cyclobutane tetracarboxylic dianhydride (CBDA) and aromatic diacid chlorides include paraphthaloyl chloride,
All above-mentioned physical properties can be well realized.
However, comparative example 1 has the high transparency measured at the 388nm of short wavelength region compared to the examples, and have
There is low modulus.In addition, comparative example 2 has high yellow colour index compared to the examples, comparative example 4 has in short wavelength region 388nm
The high transparency that place measures, and there is low modulus.In addition, comparative example 5 and `6 have in short wavelength region compared to the examples,
The high transparency measured at 388nm, or there is very high yellow colour index, and there is low modulus.
Polyamidoimide film according to the present invention can have excellent mechanical-physical character, while in the complete of visible light
There is low yellow colour index and excellent light transmittance in wavelength region, and realize low-transmittance in short wavelength region.
Particularly, since high-modulus may be implemented in polyamidoimide film, and there is low light transmission in short wavelength region
Rate, it is possible to prevent include polyamidoimide film display understructure in occur by exposure to ultraviolet light and
Caused damage, therefore, polyamidoimide film can be applied to various display fields.
Meanwhile polyamidoimide film can significantly improve modulus, and realize excellent mechanical strength, to be applied to wrap
Include the various fields of display.
Hereinbefore, although describing the present invention by specific embodiment and specific exemplary embodiment,
Them are provided just for the sake of helping to be fully understood by the present invention.Therefore, the present invention is not limited to exemplary implementation schemes, and this
The technical staff of field that the present invention belongs to can carry out various modifications and change according to this specification.
Therefore, spirit of the invention should not necessarily be limited by the above exemplary embodiments, and appended claims and and right
It is required that equivalent or comparable all modifications are intended to and fall into the scope of the present invention and thought.
Claims (19)
1. a kind of polyamidoimide film, it includes be derived from aromatic diamine, aromatic dianhydride, alicyclic dianhydride and aromatic series
The polyamidoimide of diacid chloride, wherein the alicyclic dianhydride includes the compound indicated by following formula 1, the polyamides
The total light transmittance of amine acid imide film is 88% or higher, and the light transmittance measured at 388nm is 40% or lower:
[chemical formula 1]
Wherein R1-R4It is independently from each other hydrogen, halogen, C1-C10Alkyl or C1-C10Alkoxy.
2. polyamidoimide film according to claim 1, wherein the aromatic diamine includes 2,2 '-bis- (fluoroforms
Base)-benzidine.
3. polyamidoimide film according to claim 1, wherein the aromatic dianhydride includes 4,4 '-hexafluoros different sub- third
Base diphthalic anhydrides and biphenyltetracarboxylic dianhydride.
4. polyamidoimide film according to claim 1, wherein the aromatic diacid chlorides include paraphthaloyl chloride.
5. polyamidoimide film according to claim 1, wherein the aromatic diamine based on 100mol, the aromatic series
The content of diacid chloride is greater than 50mol.
6. polyamidoimide film according to claim 1, wherein the aromatic diamine based on 100mol, the aromatic series
The content of dianhydride is 10-50mol.
7. polyamidoimide film according to claim 3, wherein the aromatic diamine based on 100mol, the aromatic series
The content of dianhydride is the 4,4 '-hexafluoroisopropylidenyl diphthalic anhydrides of 5-25mol and the biphenyltetracarboxyacid acid two of 5-25mol
Acid anhydride.
8. polyamidoimide film according to claim 1, wherein the aromatic diamine based on 100mol, described alicyclic
The content of dianhydride is 5-30mol.
9. polyamidoimide film according to claim 1, wherein the polyamidoimide film is with 5.0GPa or more
High modulus, the modulus are measured by using the UTM 3365 purchased from Instron with the tensile speed of 25mm/min.
10. polyamidoimide film according to claim 1, wherein the polyamidoimide film has according to ASTM
3.0 or the lower yellow colour index that E313 standard measures.
11. polyamidoimide film according to claim 9, wherein the polyamidoimide film is with 5.0GPa or more
High modulus, the modulus are with a thickness of 55 μm, length 50mm, width by using the UTM 3365 for being purchased from Instron
The sample of 10mm is measured with the tensile speed of 25mm/min.
12. polyamidoimide film according to claim 1, wherein based on 55 μm of thickness, the polyamidoimide
The total light transmittance of film is 88% or higher.
13. polyamidoimide film according to claim 10, wherein based on 55 μm of thickness, the polyamidoimide
Film has 3.0 or the lower yellow colour index measured according to ASTM E313 standard.
14. polyamidoimide film according to claim 1, wherein based on 55 μm of thickness, the polyamidoimide
The light transmittance that film is measured at 388nm is 40% or lower.
15. a kind of image display device, it includes the polyamidoimide films described in any one of claim 1-14.
16. a kind of polyamic acid tree derived from aromatic diamine, aromatic dianhydride, alicyclic dianhydride and aromatic diacid chlorides
Rouge, wherein the alicyclic dianhydride includes the compound indicated by following formula 1:
[chemical formula 1]
Wherein R1-R4It is independently from each other hydrogen, halogen, C1-C10Alkyl or C1-C10Alkoxy.
17. polyamic acid resin according to claim 16, wherein the aromatic diamine includes 2,2 '-bis- (fluoroforms
Base)-benzidine.
18. polyamic acid resin according to claim 16, wherein the aromatic dianhydride includes 4,4 '-hexafluoros different sub- third
Base diphthalic anhydrides and biphenyltetracarboxylic dianhydride.
19. polyamic acid resin according to claim 16, wherein the aromatic diacid chlorides include paraphthaloyl chloride.
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| KR1020170116249A KR102386217B1 (en) | 2017-09-12 | 2017-09-12 | Polyamic acid resin and polyamideimde film |
| KR10-2017-0116249 | 2017-09-12 |
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| CN109486188A true CN109486188A (en) | 2019-03-19 |
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|---|---|---|---|
| CN201811043008.0A Active CN109486188B (en) | 2017-09-12 | 2018-09-07 | Polyamide acid resin and polyamide imide film |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US10815378B2 (en) |
| KR (1) | KR102386217B1 (en) |
| CN (1) | CN109486188B (en) |
| TW (1) | TWI842677B (en) |
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| CN113906086A (en) * | 2019-05-31 | 2022-01-07 | Sk新技术株式会社 | Polyamide-imide film |
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| CN113906086A (en) * | 2019-05-31 | 2022-01-07 | Sk新技术株式会社 | Polyamide-imide film |
| CN112251021A (en) * | 2019-07-05 | 2021-01-22 | Sk新技术株式会社 | Polyimide-based film, film for covering window, and display device including the film for covering window |
| CN112251021B (en) * | 2019-07-05 | 2024-05-03 | Sk新技术株式会社 | Polyimide film, film for covering window, and display device including the film for covering window |
| CN112480443A (en) * | 2019-09-12 | 2021-03-12 | 杜邦电子公司 | Polyimide film and electronic device |
| CN113539082A (en) * | 2020-04-14 | 2021-10-22 | Sk新技术株式会社 | Window covering film and flexible display panel comprising same |
| CN113429785A (en) * | 2021-06-16 | 2021-09-24 | 浙江中科玖源新材料有限公司 | Low-birefringence polyimide film and preparation method thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| US10815378B2 (en) | 2020-10-27 |
| KR102386217B1 (en) | 2022-04-13 |
| TWI842677B (en) | 2024-05-21 |
| TW201912681A (en) | 2019-04-01 |
| CN109486188B (en) | 2022-11-11 |
| US20190077960A1 (en) | 2019-03-14 |
| KR20190029110A (en) | 2019-03-20 |
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